A novel approach for the analysis of dissolved lignin in freshwaters is presented. Lignin concentrations in natural water samples are low, and a lignin extraction is usually required to obtain sufficient material for analysis. In this study, the alkaline CuO oxidation, which liberates a set of lignin-derived phenols, is performed directly on 15 mL of water sample in a microwave digestion system, hence reducing the required sample amount and preparation time considerably. These features make the method particularly suitable to study diagenetic changes of dissolved lignin in small-scale laboratory or field experiments. Phenol separation and quantification by gas chromatography tandem mass spectrometry lead to method detection limits between 22.7 and 1260 ng/L for single phenols, which corresponds to minimum lignin concentrations in the range of 8.5 μg/L (Σ), offering applications for wetland, river, and lake waters with high terrestrial dissolved organic matter inputs. As a general method improvement, we present the addition of EDTA during phenol workup. EDTA binds remaining copper, thereby speeding up sample flow through the solid phase sorbent during phenol extraction and, furthermore, prevents substantial phenol losses, which occur if a water sample contains nitrate. Three natural water samples, a fresh leaf leachate and two humic-rich lake waters, were analyzed by the direct method presented here and in comparison with the established C18 extraction approach. Results show a similar reproducibility of both methods but reveal lower absolute lignin phenol yields in the humic-rich lake water samples upon C18 extraction.

Abstract. Phragmites australis litters were incubated in three waterlogged anoxic wetland soils of different nutrient status for 75 d, and litter nitrogen (N) dynamics were analyzed by elemental analyses and Fourier transform infrared spectroscopy (FTIR). At the end of the incubation time, the N content in the remaining litter tissue had increased in most samples. Yet, the increase in N content was less pronounced when litters had been decomposed in a more-N-poor environment. FTIR was used to quantify the relative content of proteins in litter tissue and revealed a highly linear relationship between bulk N content and protein content. Changes in bulk N content thus paralleled and probably were governed by changes in litter protein content. Such changes are the result of two competing processes within decomposing litter: enzymatic protein depolymerization as a part of the litter breakdown process and microbial protein synthesis as a part of microbial biomass growth within the litter. Assuming microbial homeostasis, DNA signals in FTIR spectra were used to calculate the amount of microbial N in decomposed litter which ranged from 14 % to 42 % of the total litter N for all leaf samples. Microbial carbon (C) content and resultant calculated carbon use efficiencies (CUEs) indicate that microbial N in litter accumulated according to predictions of the stoichiometric decomposition theory. Subtracting microbial C and N contributions from litter, however, revealed site-dependent variations in the percentual amount of the remaining still-unprocessed plant N in litter compared to remaining plant C, an indicator for preferential protein depolymerization. For all leaf litters, the coefficient of preferential protein depolymerization (α), which relates N-compound depolymerization to C-compound depolymerization, ranged from 0.74–0.88 in a nutrient-rich detritus mud to 1.38–1.82 in Sphagnum peat, the most nutrient-poor substrate in this experiment. Preferential protein depolymerization from litter decomposing in Sphagnum peat leads to a gradual N depletion in the early phase of litter decomposition, which we propose as a preservation mechanism for vascular litter in Sphagnum peatlands.

The occurrence and distribution of organochlorine pesticides (OCPs) in aquatic systems is a matter of global concern and poses significant toxicological threats to both organisms and human health. Despite the extensive use of OCPs for pest and disease control in southern Africa, relatively few studies have examined the occurrence and toxicological risks of OCP residues in the region. This study investigates the composition, distribution, and potential sources of OCP contamination in sediments from Richards Bay, a rapidly developing industrial port on the northeast coast of South Africa. Surface sediments collected from Richards Bay Harbour and surrounding areas indicate that OCP contamination in the region is widespread. Total concentrations (∑OCP) in surface samples ranged from 135 to 1020 ng g−1, with hexachlorocyclohexanes (∑HCH; 35–230 ng g−1) and dichlorodiphenyltrichloroethanes (∑DDT; 12–350 ng g−1) the dominant contaminant groups detected. Metabolite isomeric compositions indicate that the presence of aldrin and endosulfan likely result from historical agricultural usage, while recent input of γ-HCH, heptachlor, and endrin may be linked to the illegal use of old pesticide stockpiles. Total DDT concentrations were dominated by p,p′-DDT (80 ± 64 ng g−1), which was attributed to its ongoing use in malaria vector control in the region. A 210Pb-dated sediment core revealed that OCP input to the local environment increased dramatically from relatively low concentrations in the mid-1940s (∑OCP, 355 ng g−1) to peak levels (∑OCP, 781 ng g−1) in the 1980s/1990s. An overall decrease in ∑OCP concentration from the mid-2000s is likely related to restrictions on use following the Stockholm Convention in 2004. Despite current restrictions on use, OCP concentrations exceeded sediment quality guidelines in the vast majority of cases, raising concerns for protected estuarine and mangrove habitats in the area, as well as for local fishing and farming communities.

<p><strong>Abstract.</strong> Nitrogen (N) dynamics in <i>Phragmites australis</i> litter due to anaerobic decomposition in three anoxic wetland substrates were analyzed by elemental analyses and infrared spectroscopy (FTIR). After 75 days of decomposition, a relative accumulation of bulk N was detected in most litters, but N accumulated less when decomposition took place in a more N-poor environment. FTIR was used to quantify the relative content of proteins in litter tissue and revealed a highly linear relationship between bulk N content and protein content. Changes in bulk N content thus paralleled and probably were governed by changes in litter protein content. Such changes are the result of two competing processes within decomposing litter: enzymatic protein depolymerization as a part of the litter breakdown process and microbial protein synthesis as a part of microbial biomass growth within the litter. Assuming microbial homeostasis, DNA signals in FTIR spectra were used to calculate the amount of microbial N in decomposed litter which ranged from 14 to 42 % of the total litter N for all leaf samples. Microbial carbon (C) content and resultant calculated carbon-use efficiencies (CUEs) indicate that microbial N in litter accumulated according to predictions of the stoichiometric decomposition theory. Subtracting microbial C- and N-contributions from litter, however, revealed decomposition site dependent variations in the percentual amount of remaining, still unprocessed plant N compared to remaining plant C, an indicator for preferential protein depolymerization. For all leaf litters, the coefficient of preferential protein depolymerization (α), which relates N-compound depolymerization to C-compound depolymerization, ranged from 0.74–0.88 in a nutrient-rich detritus mud to 1.38–1.82 in <i>Sphagnum</i> peat, the most nutrient-poor substrate in this experiment. Preferential protein depolymerization leads to a gradual N depletion of decomposing litter which we propose as a preservation mechanism for vascular litter decomposing in <i>Sphagnum</i> peat.</p>